Organo-siloxanes and method of



Patented Jan. 11, 1949 2,458,944 ORGANO-SILOXANES ANDMETHOD F. MAKING THEM James Franklin Hyde, Corning, N. Y., assignor to Corning Glass Works, Corning,

poration of New York No Drawing. Application March 20, 1944, fSerialNo.527,349

This invention relates to new compositions of matterand their preparation and, more particularly, to organo-siloxanes and methods of preparing them.

This application is a continuation-in-part of my copending applications Serial Number 432,528 filed February 26, 1942, Serial Number 467,146 filed November 27, 1942 and Serial Number 483,- 450, filed April 17, 1943, now abandoned, all assigned to the assignee of the present invention. l l r The hydrolysis of a mono-silane of the type SiX4, where X is a hydrolyzable radical, such as halogen, alkoxy, aroxy, acyloxy, hydrogen, etc., does not result in a simple hydroxy compound but produces instead a brittle, insoluble, infusible siliceous solid comprising a three-dimensional network of structural units composed of siloxane linkages as a result of the concurrent or subsequent loss of water from the 'intermediately' I formed hydroxy compound.

halogen, acyloxy or alkoxy and subsequent "811m?- ination of hydrogen' halide,carboxylic acid or alcohol, respectively. .Such eliminations are catalyzed by mineral acids. especially. hydrochloric and sulphuric and by alkali metal hydroxides, especially sodium hydroxide. It is apparent that, in the formation of such a rigid structure, many hydroxyl groups become isolated and block some of the possible cross-link-. ages. As the structural network becomes more complicated, dehydration becomes increasingly more difiicult, and the result is a partially dehydrated siliceous mass of "poor dimensional stability. I

Organo-substituted silanes of the type RR'SiYz are prepared by means 0i the well-known Grignard reaction, where Rand B. may be any organic radical which is capable of reacting with magnesium to form a Grignard reagent and which is attached to silicon through .a carbon atom, and where each Y is a hydrolyzable radical such. as hydrogen, halogens, alkoxy,. aroxy, acyloxy, etc. By hydrolyzable radical isj meant, in general, any, radical which is attached to sili- 6 Claims. (Cl. 260-465) con by other than carbon-silicon linkage and which under thesame setof conditions is more readily hydrolyzed than an organic radical direet- 1y attached to silicon through carbon-silicon linkage. A f

siloxanes can comprise only chain and cyclic structures. Intermediate crystalline dihydroxy compounds can in some instances beisolated. The final products whichlare usually resinous in character bear little physical resemblance to silicic acids but are .closely related thereto in chemical structure, difiering only in the restric,-

tion of possible silograne linkages to two dimensions instead of three;

Organoesubstituted silanes of R"R,"'R".'S1Z. may also .be prepared the Grignard reaction where Rf, RJ"v and R" are organic radicals which are capable. of reacting withmagnesiunihto' form a ,Grignard reagent, and which'are not necessarilyjthe same, and

where Z is ,a hydrolyzable radical such as X and Y defined above. When these silanes are, hydro lyzed and dehydrated, they yield simple oxides in the structural unit of' which three of the four silicon bonds are blocked ,by ,the organic radicalsRff, R' and R". I I

In this case, ease of hydrolysis is further diminished and in some cases the intermediatehy droxy-silanes can be isolated. The completely dehydrated product is .dimeric .because only one siloxane linkage can be formed. The dimers are either crystalline or liquid. N H

Priorattempts to utilize the above-described reactions have not contemplated combinations thereof, but have beenconfined more or less to the individual reactions and their products. Such .products, as shownabove, have limited utility and the range .of properties obtainable in the products of a given typecf, reaction is the type relatively restricted. For example, the product resulting from Type I reaction is an insoluble, infusible gel of little utility; Type III reaction yields generally inert liquid products which, although a e b e n ni s ent can? not be polyrnerized beyond the dimer and: hence cannot be utilized per se for coating composi tions, resinous impregnants and the like.

An object of this invention is the production of new and useful products from these'ireactions. which will have desirable predetermined properties.

Another object is to combine the ahovedescribed reactions and thus to inter-condense the hydrolysis products of at least one ,no n -org ano substituted mono-silane, at least one di'-organo-, substituted mono-silane and at least onetriorgano-substituted mono-silane.

Another object is to produce liquid products of am na, sc s t Ano h r; i t is. o: redu e ermo las inwsnrq uq s- Another ject e p uce thermosetting resinous products.

A further object of-thepresent invention is to prepare qrgano-siloxanes, which contain silicon atoms having no organic radicals attached thereto through carbon-silicon;linkages, and silicon atoms having two and three organic radicals respectively. attached thereto through carbon-siliqn ialese v W o ,cq pris s mi lna e her t least, one. compound. of each.- ci the, types-S119, RBISiYz, andv RiR"'R""SiZ, wherejR, R", R, 3 Q'R e ha m i e en Ea-E4 9. a li a ttach tqsi i nth e shr e qnr il qn. ie asse nd he e Y W er r he r. dif e n r yzable-t als tiaehed q il g i' n 'heiiea a on: ilie i in e es dl au i a ther tohydrolyzetogether and tQbec m e inter; condensed. It is. to be understoodthat each of" mes-levees R e snt a Wa s w-2 s Quanti 7 r in amount suflicient to produg aperpe ti iegeg ct qrpthe prcperties of the,res ,ulting,.inter ondena m thq l'c acq mnll m si nten w r. densation isby introducingv intothefrnixture by. amu a dition h e the mo nt w er. wh m s al ula e seme h drol s s i. theym xture nd hich pref r hlyi isso vedj n ree. W .30% olume c m lvent. 1 t a lcoho i xani a a iq ace onaem Although. a difference in the. reactivity of Qthe. various individualftypes of, hydr oly zable com Wun e an i ne ian n the.- m n s r en in the initial mixtura maymakedt desirahleto vary the conditions o f th e process, as will appear from a consideration ofi the accompanying examples, the above recited'procedure in general isto bgpr eferred, The use.,of. a water-miscible solvent for diluting the hydrolyzablemixture or the water or both and the dropwise addition of the, i e-, nsu e hemam enae e of. hemose: neity.duringhydrolysis; Under these conditionsv q eneatim or h o m o f. ilenc 12 s,-

Ow 's oee r n yitame.hy uu isbvt it isfio baunderstoodthat the extent; of furthgr subsequent dehydration isopticnal and will depend; largely 9 1. K 7 q. hl ll 11 2 9413 t me h dr iqn f he we e m x: ture 0f; mono silanes result in intercondensation mistre tment nt r-e e as n x n nka be w en he i e n, a m f. h matsx. e1 -v ariety f he ubs i u ed Q anie adie ls is limited only by their ability to form a Grignard reagent. The radicals which may thus be substituted may include alkyl radicals such as methyl, ethyl, propyl isopropyl, butyl, isobutyl, amyl, hexyl, heptyl to octadecyl and higher; alicyclic radicalasuch asscyclopentyl, cyclohexyl, etc., aryl and'alkaryl' radicals such as phenyl, monoand poly-alkyl phenyls as tolyl, xylyl, mesityl, mono-, Cllr, and tri-ethyl phenyls, mono-, di-, and tripropyl phenyls, etc.; naphthyl, monoand polyallrylg naphthyls, as methyl naphthyl, diethyl naphthyl, tri-propyl naphthyl, etc.; tetra-hydronaphthyl; anthracyl, etc.; aralkyl such as benzyl, phenylethyl, etc. alkenyl such as methallyl, allyl, etc. The aboveradicals may contain inorganic suhstituents such, as halogens, etc.

If thehydrolyzable group or groups of all of the silanes in the mixture to be hydrolyzed are halogens, it is preferable to employ dioxan as the solvent because it is inert to the halogens. t' he m x n eq nteinse h aloge a n al groups the formcr, can :betconverted to. the latter.

th 9% ddit onr x1 1 tether mix-i ture, or the mixture can be diluted with dioxan,

n re te z withv ue s ph W n t mi tur curta n Qnlr l sqxr' ip n nr' e miscible solvent may? be used together withja; ace qf a rlisuh- S:-H M5 a a s i h s case, alcoholzmay beipreferred on account of its relatiyely;1ow;cost llf lix ture s of water miscible.

solvents may be used.

Intheahgvadescribed method, the slow incorporation of; water, into the homogeneous, solution; insures that hydl'plysisisnotrpermitted to proceed:

unchecked, whereby the more reactiveisi laneor silanes wouldbe morecompletelyhydrolyzed and;

. reactive silanes thanwould heithe. case if the hydrolysis were conducted rapidly. Under these circumstances, simultaneous condensation of the various intermediate hydroxy compounds takes place and an intimate inter-mo]ecularcombina tion through siloxane linkages of silicon atoms bearing different numbers and kinds of organic radicals becomes possible to the fullest extenti This insures a. true inter-condensation with the formation of homogeneous products containing mixed unit structures;

After removal oi solvent and'excess water-theli'ydrolysis products resulting from the above process" are water-immiscible liquids ofvarying: viscosity. They are soluble in the common or.- anic' solventsfsuch as benzene, toluene, etc. Many of them are thermoplastic, some are thermosetting, and' some are thermally stable liquids. Further condensation and polyrnerization may-be brought about by heating, which generally results in an increase in viscosity and in some cases, ifv carried to completion, results in resinous solid products, The desired'degree of polymerization will depend largely upon the'contemplateduse of the product and may be varied at will, since thefinal physical properties depend directly-on the total number of "siloxane linkages per molecule and th e disposition of the siloxane linkages, this heing controlled-by the relative amounts of the various types of f silanes initially present.

he a ially de y ate qrgawsiloxanes or hydrolysis products, after, removal of solvents, are generally. liquids of various viscosities and they varyinthe extent tc which dehydration has occurredfat this; stage, The ease of dehydration and the physical properties oi the completelycondensed organo-siloxanes vary with the kind the molecular size of the organic radical or radi-- cals present and the number of possible siloxane linkages, that is, the final oxygen to silicon ratio. Products containing methyl radicals dehydrate more readily than those containing ethyl, propyl,

etc., radicals or phenyl radicals and in general products containing alkyl radicals dehydrate more readily than those containing aryl radicals. number of radicals per silicon atom increases or as the final oxygen to silicon ratio decreases.

When this ratio is less than 0ne,.the organosiloxanes are oils of relatively low viscosity. Their volatility decreases with increasing molecular size of the radicals and at the same time the viscosity may increase somewhat. As the final oxygen to silicon ratio increases from 1.0 to 1.3; there is a corresponding increase in molecular complexity or the number of siloxane linkages and an accompanying increase in viscosity. When the ratio is in the neighborhood of 1.3 and aryl radicals predominate, the viscosity increases to such an extent that the organo-siloxanes are thermoplastic solids which may be 'fused and solidified repeatedly by heating and cooling. As the oxygen to silicon ratio is increasedto the neighborhood of 1.5 and beyond (approaching 2), the organo-siloxanes tend to become thermosetting and more particularly if the molecular size of the radicals is decreased.

Thus it will be seen that uniformity of behavior not only makes possible a wide variation in propertiesof the compositions, including viscosity, vapor pressure, melting range, setting rate, hardness, toughness, etc., but it also enables one to predict the most suitable combination of intermediate compounds for the production of an organo-siloxane for the desired purpose.

The organo-siloxanes which are produced by my method may be represented as combinations of the units i and R" R R"" Sibearing in mind that these units are chemically combined with each other by siloxane linkages, that the percentage of each unit may be varied at will, and that the properties of the resulting products will show corresponding variations which can be predicted in making compositions for a particular purpose. It is also to be understood that the units may be joined in a multiplicity of ways to form chain and cyclic structures and combinations thereof. Also, the organic radical or radicals in each structural unit may be varied in kind. N

The following examples will illustrate the m'ode of operation of the process and the character of the resulting products.

ratio 3/3/1 and three volumes of 'dioxane were added. Solution was complete when the-mixture was warmed. 0.5% H01 diluted with dioxane was Ease of dehydration also increases as the added dropwise, The solution was concentrated to leave a tacky solid, which was thermoplastic,

but which set in one hour at C.

Example 2 A- mixture of SMOCgHsM. 19.7 grams (.09) mol), (CsH5)2 SiClz, 24.48 (.09 mol), and (CH3)3 Si(OC2Hs), 3.5 grams (.03 mol) was prepared.-

The mixture was stirred and treated dropwise with 5.13 grams of water over a period of 45 minutes to bring about hydrolysis. After adding the above amount of water (which is that theoretically required for complete hydrolysis) another gram of water was added and the reaction mixture allowed to stand overnight. After again stirring the reaction mixture for a few minutes, it was heated to boiling for 5-10 minutes and then washed to neutrality using diethyl ether as a solvent. Thesolvent and residual water were then removed under vacuum with warming, leaving an extremely viscous, tacky liquid weighing 26.67 grams. It was very fluid at and after 3 hours at that temperature it had become slightly more viscous. At room temperature it was nontacky though still plastic. Heating for three hours at 250 C. caused the product to set to a resinous solid, 1

' Example 3 A mixture of 20.4 grams of S1014 (0.12 mol), 24.6 grams of (C'cHs) (CaHs) SiClz (0.12 mol) and 6.02 grams of (C2He)3 SiCl (.04 mol) was prepared. On adding the first drops of water with stirrin slight precipitation occurred, so the mixture was diluted with 40 cc. of dioxan. The water to be added was also diluted with 20 cc. of dioxan. Hydrolysis of the halide mixture was then carried out by adding the dioxan-Water mixture (containing 6.84 grams of water) to the halide mixture over a period of 6 hours. Some further precipitation of silica occurred amountingin toto to 4 grams. The silica equivalent of the initial SiC14 was 7 .2 grams. An oily liquid was obtained which when washed and dried had a viscosity of 11,780 centistokes. When the product was heated at 190 C. for 3 hours there was very little viscosity increase but after 18 hours at 250 it had set to a hard and tough resinous solid.. 1

Example 4 the secondary effect of the size of the organic radicals. .However, in all organic-silicon compounds the thermal stability of the carbon-silicon linkage varies with the kind of radical. It is necessary to take this into account when considering uses for organo-siloxanes. In general, there is a decrease in thermal stability with increase in size of aliphatic radicals. This is clearly shown by comparison of the thermal behavior of organssiloxanes containing methyl radicals with those containing dodecyl radicals. The compositions containing allyl, methallyl, benzyl and. p-phenylethyl radicals, are relatively less stable-than compositions containing such radicals as phenyl, methyl, ethyl, etc. Therefore, certain temperature limitations are encountered in their uses.

It will be seen that the inter-condensates produced by my method are not mixtures of individual organo-siloxanes but are new compounds diffe'ring therefrom in homogeneity of structure and properties. It will further be seen that the new organo-siloxanes may contain various different radicals attached to the same silicon atom and the individual silicon atoms may differ in: the number and kind of radicals attached thereto in which respect the new silo'xanes diif'e'r fromprevh ous siloxanes where each silicon atom. was attached to the same kind of radicals. Such difierences result in new compounds or inter-condem sates which embody various improvements over previous organo-silo'xanes with respect to temperature coefiicient of change of viscosity, thermal resistivity, chemical stability, electrical; properties, etc.

The organo-siloxanes produced by my method may be adapted to various uses and for anyspecific use the physical properties and character'- istics of the product can be controlled by the proper selection of the initial starting materials so as to obtain the desired oxygen to silicon ratio and a suitable variety of radicals attached to the silicon atom. Products which remain liquid with little or no tendency for further polymerizationeven at elevated temperatures include products having an oxygen to silicon ratio between 0.5 and 1.0 and particularly those containing lower alkyl' Such products have good electrical radicals. properties whereby they may be used as the liquid filling medium for transformers, circuitbreakers, submarine cables, condensers, etc. In general these products have an unusually low coefiicient of change of viscosity with temperature and may find use in hydraulic pressure systems which are subjected to wide changes of temperatures or as lubricants for systems of moving parts operating under subnormal or abnormal temperatures.

More viscous liquid products such as those wherein the oxygen to silicon ratio lies in the neighborhood of 1.0 or more may also be used for lubricants and are particularly useful as damping media in delicate instruments and 'th'e like.

Thermoplastic and thermosetting products having an oxygen-silicon ratio usually greater than 1.0 are useful as molding compounds, fi-lm forming coatings, varnishes, impregnating agents for electrical insulation and the like. They may be applied as solutions of the incompletely condensed organo-siloxanes and after evaporation of the solvent can be further polymerized in situ. The more brittle products should be useful embedding media for condenser plates as well as molding compounds. Such products usually have an oxygen-silicon ratio of 1.5 or greater and may be thermoset in situ by heat.

I claim:

1. An organo-siloxane consisting essentially of oxygen atoms and units which correspond substantially to the general formulae =Si'=, FIR/Si: and R 'R *R' Si-, respectively, sa'i'd units being the only silicon units present in said siloxane and being joined to each other by said oxygen atoms through silicon-oxygen linkageswhereR, R R. R and R"" are mono-valent hydrocarbeniradicals which are attached to silicon through carbon-silicon linkages and where the remaining valences oi the silicon atoms are satisfied by said silicon-oxygen linkages.

- 2; An orgasm-siloxane consisting essentially of: oxygen atoms. and units which correspond subsiloxane and. being joined together by said oxygen atoms through silicon-oxygen linkages, where some. of the His are lower alkyl radicals and-therest are phenyl radicals, said radicals being attached to silicon through carbon-silicon linkages and where the remaining valences of the silicon atoms are satisfied. by said silicon-oxygen linkages.

4. An organo-siloxane consisting essentially of oxygen. atoms: and units. which correspond substantially to. the general formulae =Si=', (CI-1928i: and (CH3) 3Si, respectively, said units being the only silicon units present in said siloxane and being joined toeach other by oxygen atoms through silicon-oxygen linkages and the remaining valences of the silicon atoms being satisfied by said silicon-oxygen linkages.

' 5.. Anorgano-siloxane consisting essentially of oxygen atoms and units which correspond substant-ially to the formulae =Si=, (CcHshSi: and ((;I-I.i)aSi,v respectively, said units being the only silicon units presentin said siloxane and beingjoined to each other by said oxygen atoms through silicon-oxygen linkages and the remaining valences of the silicon atoms being satisfied by saidsilicon-oxygen linkages.

6. An organo-si-loxane consisting essentially of oxygen atoms and units which correspond substantially to the formulae Si=, (OBI-I5) (Cal-I5) Si: and (C2H5)zSi-, respectively, said units being the only silicon units present in said siloxane and being joined to each other by said oxygen atoms through silicon-oxygen linkages and the remaining valences ofthe silicon atoms being sati-f-ied by said silicon-oxygen linkages.

JAMES FRANKLIN HYDE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,258,218 Rochow Oct. '7, 1941 2,258,220 Rochow Oct. '7, 1941 2,258,222 Rochow Oct. 7, 1941 2,371,068 Rochow Mar; 6, 1945 OTHER REFERENCES Meads et al.: Trans. Journal of the Chemical Soc. (London), vol. 105, 1'9'14, pp. 679 to 690.

:Rochow: Chemistry of the Sil'iconcs, Wiley, 1946,.pp. 93 and 94.

Cusa-et al.-: J. Chem. Soc. (London), 1932, pp. 2205 to2209. 

